CN104918906A - Partially fluorinated compounds - Google Patents
Partially fluorinated compounds Download PDFInfo
- Publication number
- CN104918906A CN104918906A CN201380065626.4A CN201380065626A CN104918906A CN 104918906 A CN104918906 A CN 104918906A CN 201380065626 A CN201380065626 A CN 201380065626A CN 104918906 A CN104918906 A CN 104918906A
- Authority
- CN
- China
- Prior art keywords
- compound
- fluorinated
- partially fluorinated
- olefinic monomer
- diiodo
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 150000001875 compounds Chemical class 0.000 title claims abstract description 86
- 238000000034 method Methods 0.000 claims abstract description 69
- 239000000203 mixture Substances 0.000 claims abstract description 38
- 239000000178 monomer Substances 0.000 claims description 76
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 claims description 55
- 239000000126 substance Substances 0.000 claims description 36
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims description 29
- 229920000642 polymer Polymers 0.000 claims description 27
- 239000003999 initiator Substances 0.000 claims description 23
- 239000012986 chain transfer agent Substances 0.000 claims description 19
- 238000006116 polymerization reaction Methods 0.000 claims description 18
- UUAGAQFQZIEFAH-UHFFFAOYSA-N chlorotrifluoroethylene Chemical group FC(F)=C(F)Cl UUAGAQFQZIEFAH-UHFFFAOYSA-N 0.000 claims description 7
- 239000000376 reactant Substances 0.000 claims description 6
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical compound FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 claims description 5
- MIZLGWKEZAPEFJ-UHFFFAOYSA-N 1,1,2-trifluoroethene Chemical group FC=C(F)F MIZLGWKEZAPEFJ-UHFFFAOYSA-N 0.000 claims description 4
- YFUMKDXIKGOQDA-UHFFFAOYSA-N 1-ethenoxy-3-methoxypropane Chemical compound COCCCOC=C YFUMKDXIKGOQDA-UHFFFAOYSA-N 0.000 claims description 4
- OVGRCEFMXPHEBL-UHFFFAOYSA-N 1-ethenoxypropane Chemical compound CCCOC=C OVGRCEFMXPHEBL-UHFFFAOYSA-N 0.000 claims description 4
- XREZAPYWZGJIFS-UHFFFAOYSA-N ethenoxymethoxyethane Chemical compound CCOCOC=C XREZAPYWZGJIFS-UHFFFAOYSA-N 0.000 claims description 4
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical compound COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 0.000 claims description 4
- 239000007795 chemical reaction product Substances 0.000 claims description 3
- LVTJOONKWUXEFR-FZRMHRINSA-N protoneodioscin Natural products O(C[C@@H](CC[C@]1(O)[C@H](C)[C@@H]2[C@]3(C)[C@H]([C@H]4[C@@H]([C@]5(C)C(=CC4)C[C@@H](O[C@@H]4[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@@H](O)[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@H](CO)O4)CC5)CC3)C[C@@H]2O1)C)[C@H]1[C@H](O)[C@H](O)[C@H](O)[C@@H](CO)O1 LVTJOONKWUXEFR-FZRMHRINSA-N 0.000 claims description 3
- 230000000379 polymerizing effect Effects 0.000 abstract 1
- -1 fluorine iodo compound Chemical class 0.000 description 36
- 238000006243 chemical reaction Methods 0.000 description 29
- 229920002313 fluoropolymer Polymers 0.000 description 21
- 239000004811 fluoropolymer Substances 0.000 description 21
- 229910052740 iodine Inorganic materials 0.000 description 21
- 239000011630 iodine Substances 0.000 description 21
- 229910052799 carbon Inorganic materials 0.000 description 18
- 238000002360 preparation method Methods 0.000 description 17
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- 239000002253 acid Substances 0.000 description 11
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 10
- 239000003513 alkali Substances 0.000 description 10
- 150000002978 peroxides Chemical class 0.000 description 10
- 150000003839 salts Chemical class 0.000 description 10
- 239000013078 crystal Substances 0.000 description 9
- 229910052731 fluorine Inorganic materials 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- 239000000523 sample Substances 0.000 description 9
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 8
- 238000005914 dehydroiodination reaction Methods 0.000 description 8
- 239000003995 emulsifying agent Substances 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 239000006185 dispersion Substances 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 7
- 229920001973 fluoroelastomer Polymers 0.000 description 7
- 238000007711 solidification Methods 0.000 description 7
- 230000008023 solidification Effects 0.000 description 7
- UZKWTJUDCOPSNM-UHFFFAOYSA-N 1-ethenoxybutane Chemical compound CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 6
- 239000012752 auxiliary agent Substances 0.000 description 6
- 239000012153 distilled water Substances 0.000 description 6
- FJKIXWOMBXYWOQ-UHFFFAOYSA-N ethenoxyethane Chemical compound CCOC=C FJKIXWOMBXYWOQ-UHFFFAOYSA-N 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 238000007789 sealing Methods 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 238000009835 boiling Methods 0.000 description 5
- 239000011737 fluorine Substances 0.000 description 5
- 125000001153 fluoro group Chemical group F* 0.000 description 5
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 5
- 239000004816 latex Substances 0.000 description 5
- 229920000126 latex Polymers 0.000 description 5
- 125000005647 linker group Chemical group 0.000 description 5
- 229910044991 metal oxide Inorganic materials 0.000 description 5
- 150000004706 metal oxides Chemical class 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 4
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- 150000001336 alkenes Chemical class 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000007720 emulsion polymerization reaction Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 4
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 150000003863 ammonium salts Chemical class 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000001273 butane Substances 0.000 description 3
- 150000001721 carbon Chemical group 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000007334 copolymerization reaction Methods 0.000 description 3
- 229920001971 elastomer Polymers 0.000 description 3
- 239000003292 glue Substances 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- 238000003780 insertion Methods 0.000 description 3
- 230000037431 insertion Effects 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 239000000693 micelle Substances 0.000 description 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 150000004965 peroxy acids Chemical class 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000001294 propane Substances 0.000 description 3
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- BJELTSYBAHKXRW-UHFFFAOYSA-N 2,4,6-triallyloxy-1,3,5-triazine Chemical compound C=CCOC1=NC(OCC=C)=NC(OCC=C)=N1 BJELTSYBAHKXRW-UHFFFAOYSA-N 0.000 description 2
- LEJBBGNFPAFPKQ-UHFFFAOYSA-N 2-(2-prop-2-enoyloxyethoxy)ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCCOC(=O)C=C LEJBBGNFPAFPKQ-UHFFFAOYSA-N 0.000 description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 2
- QBTUCBKAWGUMMK-UHFFFAOYSA-N C=CC.[F] Chemical group C=CC.[F] QBTUCBKAWGUMMK-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 description 2
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- VIBRUMXTFSYBCG-UHFFFAOYSA-N [F].C=CCCCC Chemical compound [F].C=CCCCC VIBRUMXTFSYBCG-UHFFFAOYSA-N 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 125000001118 alkylidene group Chemical group 0.000 description 2
- 235000019395 ammonium persulphate Nutrition 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 description 2
- USPADFUBVAGYOJ-UHFFFAOYSA-N butyl 2-ethylhexanoate Chemical group CCCCOC(=O)C(CC)CCCC USPADFUBVAGYOJ-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 235000019241 carbon black Nutrition 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 230000002153 concerted effect Effects 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000006356 dehydrogenation reaction Methods 0.000 description 2
- ZQMIGQNCOMNODD-UHFFFAOYSA-N diacetyl peroxide Chemical compound CC(=O)OOC(C)=O ZQMIGQNCOMNODD-UHFFFAOYSA-N 0.000 description 2
- 239000012933 diacyl peroxide Substances 0.000 description 2
- 150000001993 dienes Chemical class 0.000 description 2
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 229910000856 hastalloy Inorganic materials 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- PGFXOWRDDHCDTE-UHFFFAOYSA-N hexafluoropropylene oxide Chemical compound FC(F)(F)C1(F)OC1(F)F PGFXOWRDDHCDTE-UHFFFAOYSA-N 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- ICIWUVCWSCSTAQ-UHFFFAOYSA-M iodate Chemical compound [O-]I(=O)=O ICIWUVCWSCSTAQ-UHFFFAOYSA-M 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- RVZRBWKZFJCCIB-UHFFFAOYSA-N perfluorotributylamine Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)N(C(F)(F)C(F)(F)C(F)(F)C(F)(F)F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F RVZRBWKZFJCCIB-UHFFFAOYSA-N 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- QEQBMZQFDDDTPN-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy benzenecarboperoxoate Chemical compound CC(C)(C)OOOC(=O)C1=CC=CC=C1 QEQBMZQFDDDTPN-UHFFFAOYSA-N 0.000 description 1
- KDGNCLDCOVTOCS-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy propan-2-yl carbonate Chemical compound CC(C)OC(=O)OOC(C)(C)C KDGNCLDCOVTOCS-UHFFFAOYSA-N 0.000 description 1
- MPJPKEMZYOAIRN-UHFFFAOYSA-N 1,3,5-tris(2-methylprop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound CC(=C)CN1C(=O)N(CC(C)=C)C(=O)N(CC(C)=C)C1=O MPJPKEMZYOAIRN-UHFFFAOYSA-N 0.000 description 1
- IPJGAEWUPXWFPL-UHFFFAOYSA-N 1-[3-(2,5-dioxopyrrol-1-yl)phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC(N2C(C=CC2=O)=O)=C1 IPJGAEWUPXWFPL-UHFFFAOYSA-N 0.000 description 1
- LGJCFVYMIJLQJO-UHFFFAOYSA-N 1-dodecylperoxydodecane Chemical compound CCCCCCCCCCCCOOCCCCCCCCCCCC LGJCFVYMIJLQJO-UHFFFAOYSA-N 0.000 description 1
- WVGXBYVKFQJQGN-UHFFFAOYSA-N 1-tert-butylperoxy-2-propan-2-ylbenzene Chemical compound CC(C)C1=CC=CC=C1OOC(C)(C)C WVGXBYVKFQJQGN-UHFFFAOYSA-N 0.000 description 1
- DMWVYCCGCQPJEA-UHFFFAOYSA-N 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane Chemical compound CC(C)(C)OOC(C)(C)CCC(C)(C)OOC(C)(C)C DMWVYCCGCQPJEA-UHFFFAOYSA-N 0.000 description 1
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 1
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- SKVOYPCECYQZAI-UHFFFAOYSA-N 2-ethylhexyl 2-methylbutan-2-ylperoxy carbonate Chemical compound CCCCC(CC)COC(=O)OOOC(C)(C)CC SKVOYPCECYQZAI-UHFFFAOYSA-N 0.000 description 1
- BKOOMYPCSUNDGP-UHFFFAOYSA-N 2-methylbut-2-ene Chemical group CC=C(C)C BKOOMYPCSUNDGP-UHFFFAOYSA-N 0.000 description 1
- XYFRHHAYSXIKGH-UHFFFAOYSA-N 3-(5-methoxy-2-methoxycarbonyl-1h-indol-3-yl)prop-2-enoic acid Chemical compound C1=C(OC)C=C2C(C=CC(O)=O)=C(C(=O)OC)NC2=C1 XYFRHHAYSXIKGH-UHFFFAOYSA-N 0.000 description 1
- HHBBIOLEJRWIGU-UHFFFAOYSA-N 4-ethoxy-1,1,1,2,2,3,3,4,5,6,6,6-dodecafluoro-5-(trifluoromethyl)hexane Chemical compound CCOC(F)(C(F)(C(F)(F)F)C(F)(F)F)C(F)(F)C(F)(F)C(F)(F)F HHBBIOLEJRWIGU-UHFFFAOYSA-N 0.000 description 1
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
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- IYXGSMUGOJNHAZ-UHFFFAOYSA-N Ethyl malonate Chemical compound CCOC(=O)CC(=O)OCC IYXGSMUGOJNHAZ-UHFFFAOYSA-N 0.000 description 1
- VVQVXIUJLQFGGS-UHFFFAOYSA-N FC=C(F)F.[I] Chemical group FC=C(F)F.[I] VVQVXIUJLQFGGS-UHFFFAOYSA-N 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 241001441571 Hiodontidae Species 0.000 description 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 1
- WPXLSICRBPNKEI-UHFFFAOYSA-N OC(=O)OC(C)CC(C)(C)OOC(C)(C)C Chemical compound OC(=O)OC(C)CC(C)(C)OOC(C)(C)C WPXLSICRBPNKEI-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 1
- 230000018199 S phase Effects 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- USRDDBBTQMVQDV-UHFFFAOYSA-N [Br].FC=CF Chemical group [Br].FC=CF USRDDBBTQMVQDV-UHFFFAOYSA-N 0.000 description 1
- PDAVOLCVHOKLEO-UHFFFAOYSA-N acetyl benzenecarboperoxoate Chemical compound CC(=O)OOC(=O)C1=CC=CC=C1 PDAVOLCVHOKLEO-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- QUDWYFHPNIMBFC-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,2-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=CC=C1C(=O)OCC=C QUDWYFHPNIMBFC-UHFFFAOYSA-N 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- KVNRLNFWIYMESJ-UHFFFAOYSA-N butyronitrile Chemical compound CCCC#N KVNRLNFWIYMESJ-UHFFFAOYSA-N 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 235000013351 cheese Nutrition 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000005796 dehydrofluorination reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- 150000001983 dialkylethers Chemical class 0.000 description 1
- 229910000396 dipotassium phosphate Inorganic materials 0.000 description 1
- 235000019797 dipotassium phosphate Nutrition 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 description 1
- 229920001038 ethylene copolymer Polymers 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000005826 halohydrocarbons Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- DYUWTXWIYMHBQS-UHFFFAOYSA-N n-prop-2-enylprop-2-en-1-amine Chemical compound C=CCNCC=C DYUWTXWIYMHBQS-UHFFFAOYSA-N 0.000 description 1
- 125000002560 nitrile group Chemical group 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 125000006551 perfluoro alkylene group Chemical group 0.000 description 1
- YFSUTJLHUFNCNZ-UHFFFAOYSA-N perfluorooctane-1-sulfonic acid Chemical class OS(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F YFSUTJLHUFNCNZ-UHFFFAOYSA-N 0.000 description 1
- SNGREZUHAYWORS-UHFFFAOYSA-N perfluorooctanoic acid Chemical compound OC(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F SNGREZUHAYWORS-UHFFFAOYSA-N 0.000 description 1
- 238000005502 peroxidation Methods 0.000 description 1
- 150000004968 peroxymonosulfuric acids Chemical class 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000002940 repellent Effects 0.000 description 1
- 239000005871 repellent Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 239000011877 solvent mixture Substances 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- DLSMLZRPNPCXGY-UHFFFAOYSA-N tert-butylperoxy 2-ethylhexyl carbonate Chemical compound CCCCC(CC)COC(=O)OOOC(C)(C)C DLSMLZRPNPCXGY-UHFFFAOYSA-N 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- CYRMSUTZVYGINF-UHFFFAOYSA-N trichlorofluoromethane Chemical compound FC(Cl)(Cl)Cl CYRMSUTZVYGINF-UHFFFAOYSA-N 0.000 description 1
- KJWHEZXBZQXVSA-UHFFFAOYSA-N tris(prop-2-enyl) phosphite Chemical compound C=CCOP(OCC=C)OCC=C KJWHEZXBZQXVSA-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C19/00—Acyclic saturated compounds containing halogen atoms
- C07C19/08—Acyclic saturated compounds containing halogen atoms containing fluorine
- C07C19/16—Acyclic saturated compounds containing halogen atoms containing fluorine and iodine
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
- C07C17/20—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms
- C07C17/202—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms two or more compounds being involved in the reaction
- C07C17/204—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms two or more compounds being involved in the reaction the other compound being a halogen
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/25—Preparation of halogenated hydrocarbons by splitting-off hydrogen halides from halogenated hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/26—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton
- C07C17/272—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by addition reactions
- C07C17/278—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by addition reactions of only halogenated hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C21/00—Acyclic unsaturated compounds containing halogen atoms
- C07C21/02—Acyclic unsaturated compounds containing halogen atoms containing carbon-to-carbon double bonds
- C07C21/18—Acyclic unsaturated compounds containing halogen atoms containing carbon-to-carbon double bonds containing fluorine
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F214/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
- C08F214/18—Monomers containing fluorine
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
- C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
- C08F236/14—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated containing elements other than carbon and hydrogen
- C08F236/16—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated containing elements other than carbon and hydrogen containing halogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
- C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
- C08F236/14—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated containing elements other than carbon and hydrogen
- C08F236/16—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated containing elements other than carbon and hydrogen containing halogen
- C08F236/18—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated containing elements other than carbon and hydrogen containing halogen containing chlorine
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/14—Peroxides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3477—Six-membered rings
- C08K5/3492—Triazines
- C08K5/34924—Triazines containing cyanurate groups; Tautomers thereof
Abstract
Described herein is a composition comprising a partially fluorinated compound selected from the group consisting of: (a) I(CF2)XCH2CF2I; (b) ICF2CH2(CF2)XCH2CF2I; (c) I(CF2)yCH=CF2; (d) CF2=CH(CF2)yCH2CF2I; and (e) CF2=CH(CF2)yCH=CF2 wherein x is an odd integer selected from 3 to 11, and y is an integer greater than 2, along with methods of making and polymerizing such compounds.
Description
Technical field
The invention describes partially fluorinated compound together with its preparation method.These partially fluorinated compounds can be used in the preparation of fluoropolymer.
Summary of the invention
Expect to find the partially fluorinated compound of alternative in Macroscopic single crystal.In one embodiment, also expect that, for Macroscopic single crystal provides partially fluorinated compound, described partially fluorinated compound reacts quickly and/or provide higher combination in polymkeric substance.Identification prepare fluorine iodo compound comparable traditional method more effectively and/or more cheap method also will be expect.
In one aspect, provide composition, described composition comprises partially fluorinated compound, and described partially fluorinated compound is selected from:
(a)I(CF
2)
xCH
2CF
2I;
(b)ICF
2CH
2(CF
2)
xCH
2CF
2I;
(c)I(CF
2)
yCH=CF
2;
(d) CF
2=CH (CF
2)
ycH
2cF
2i; With
(e)CF
2=CH(CF
2)
yCH=CF
2
Wherein x be selected from 3 to 11 odd-integral number, and y be greater than 2 integer.
On the other hand, provide polymer composition, described polymer composition comprises the polymeric reaction product of following reactant: (a) first compound, described first compound is selected from the partially fluorinated compound of following formula: I (CF
2)
xcH
2cF
2i; ICF
2cH
2(CF
2)
xcH
2cF
2i; I (CF
2)
ycH=CF
2; CF
2=CH (CF
2)
ycH
2cF
2i; And CF
2=CH (CF
2)
ycH=CF
2, wherein x be selected from 3 to 11 odd-integral number, and y be greater than 2 integer; (b) the second compound, described second compound comprises the olefinic type monomers fluoridized.
In one aspect, provide the method preparing polymkeric substance, described method comprises: (a) provides the first fluorinated olefinic monomer, and described first fluorinated olefinic monomer comprises partially fluorinated Compound I (CF
2)
ycH=CF
2, wherein y be greater than 2 integer; Second fluorinated olefinic monomer; And initiator; And (b) makes the first fluorinated olefinic monomer and the polymerization of the second fluorinated olefinic monomer to form polymkeric substance under the existence of initiator.
On the other hand, provide the method preparing polymkeric substance, described method comprises: (a) provides the first fluorinated olefinic monomer, and described first fluorinated olefinic monomer comprises partially fluorinated Compound C F
2=CH (CF
2)
ycH=CF
2, wherein y be greater than 2 integer; Second fluorinated olefinic monomer; And initiator; And (b) makes the first fluorinated olefinic monomer and the polymerization of the second fluorinated olefinic monomer to form polymkeric substance under the existence of initiator.
On the other hand, provide the method for the partially fluorinated compound of preparation, described method comprises makes formula I (CF
2)
xthe molecule of I and vinylidene fluoride react to form I (CF
2)
xcH
2cF
2i, wherein x be selected from 3 to 11 odd-integral number.
On the other hand, provide the method for the partially fluorinated compound of preparation, described method comprises makes formula I (CF
2)
xthe molecule of I and vinylidene fluoride react to form ICF
2-CH
2(CF
2)
ycH
2cF
2i, wherein y be greater than 2 integer.
On the other hand, provide polymkeric substance, described polymkeric substance is by making following polymerization to obtain (a) first compound, and described first compound is selected from the partially fluorinated compound of following formula: I (CF
2)
xcH
2cF
2i (formula I); ICF
2cH
2(CF
2)
xcH
2cF
2i (formula II); I (CF
2)
ycH=CF
2(formula III); CF
2=CH (CF
2)
ycH
2cF
2i (formula IV); And CF
2=CH (CF
2)
ycH=CF
2(formula V), wherein x be selected from 3 to 11 odd-integral number, and y be greater than 2 integer; (b) the second compound, described second compound comprises the olefinic type monomers fluoridized.
Summary of the invention above not intended to be describes each embodiment.One or more embodiments of the detail of the present invention also illustrate in the following description.According to " embodiment " and " claims ", further feature, target and advantage will be apparent.
Embodiment
As used herein, term:
" one ", " one " and " described " are used interchangeably and refer to one or more; And
"and/or" is used to indicate one of illustrated situation or both all may occur, and such as, A and/or B comprises (A and B) and (A or B).
Term " polymer " " refer to the macromole be made up of poly-monomeric unit mutually.The poly-mutually monomeric unit that polymkeric substance comprises in a large number (such as, hundreds of or more) and there is high molecular, such as, more than 10,000 gram/mol.
In addition, the scope stated by end points herein comprises all numbers included within the scope of this (such as, 1 to 10 comprise 1.4,1.9,2.33,5.75,9.98 etc.).
In addition, the statement of " at least one " herein comprises one and larger all numbers (such as, at least 2, at least 3, at least 4, at least 6, at least 8, at least 10, at least 25, at least 50, at least 100 etc.).
Alpha, omega diiodo perfluo-alkane is important structure block in the preparation of other fluorinated compound and polymkeric substance.In fluoropolymer, alpha, omega diiodo perfluo-alkane is used as chain-transfer agent, thus contributes to the molecular weight controlling polymkeric substance.Usually, these alpha, omega diiodo perfluo-alkanes are obtained by the telomerization of tetrafluoroethylene and iodine, thus cause the CF of even number
2unit.See such as J.Org Chem., the 42nd edition, o.11,1985-1990 page (1977).In addition, iodo-compound can be grouped to polymkeric substance, and the existence of iodide in fluoropolymer can be used for being cross-linked.
There is odd number CF
2the preparation of fluoridizing diiodide of unit is difficulty and costliness always.By making ICF
2i and tetrafluoroethylene react obtained and have odd number CF
2unit fluoridize diiodide, but, tetrafluoroethylene may be difficult to process and ICF
2i is not easy to obtain.Recently, applicant has found to have odd number CF
2the preparation of the perfluorination diiodide of unit.As U. S. application 61/715, disclosed in 413 (being filed in 10-18-2012), by ethylene insertion perfluorination diiodo-compound to form the partially fluorinated diiodo-compound of odd number among other material, it can be used in Macroscopic single crystal.
Use as U. S. application 61/715, similar reaction scheme disclosed in 413 (being filed in 10-18-2012), applicant finds, vinylidene fluoride is inserted in perfluorination diiodo-compound the partially fluorinated compound of the performance that can cause having improvement in Macroscopic single crystal.
Previously, vinylidene fluoride and fluorine carbon monoiodide had reacted to obtain as United States Patent (USP) 2, and 975, the low-molecular weight polymer described in 220, it can be used as lubricant and hydraulic liquid.United States Patent (USP) 6,150,565 describe CF
2i
2with the reaction of alkene (comprising vinylidene fluoride).United States Patent (USP) 6,610,790 reactions describing perfluoroiodoalkyl hydrocarbon and vinylidene fluoride, then it reacts alkene (such as, the C fluoridized with forming section further
4f
9cH
2cF
2cH=CF
2).
In the disclosure, find, inserted by VDF in perfluorination diiodo-compound and can cause new small molecules, it can be used in fluoropolymer synthesis.This compounds can be used as chain-transfer agent, cure site monomer or the monomer even during polyreaction.In one embodiment, find, cure site monomer of the present disclosure can be more compatible with fluoroolefin comonomers, makes the counterpart of the ethylene insertion compared to them, and rapid reaction speed has higher combination.
The disclosure is intended to the preparation for partially fluorinated compound, comprises iodine, carbon-to-carbon double bond or their combination.
In the disclosure, disclose the method for the perfluor diiodide compound preparing vinylidene fluoride-replacement, wherein make perfluorination diiodo-compound and vinylidene fluoride (CH
2=CF
2) react the α fluoridized with forming section, ω-diiodo-compound.Then partially fluorinated α can be made, the iodine olefin(e) compound that ω-diiodo-compound dehydroiodination is fluoridized with forming section (namely, the side of molecule comprises end atomic iodine and on the opposite side of molecule, comprises the compound of end carbon-to-carbon double bond) and partially fluorinated diolefin compound (that is, the opposite side of molecule comprising the compound of two end carbon-to-carbon double bonds).
Hereafter show exemplary reaction of the present disclosure, wherein perfluorination diiodo-compound raw material is formula I (CF
2)
athe perfluorination α of I, ω-diiodo-alkane, wherein a be greater than 2 and be not more than 20 integer (such as, a is 3,4,5,6,7,8,9,10,11,12,13,14,15,16,17,18,19 or 20).Should be noted, although following reaction scheme starts with perfluorination α, ω-diiodo-alkane and straight-chain paraffin and the normal olefine compound of gained is shown, when using other perfluorination diiodo-compound, can the similarly principles of chemistry described in application method I-III.
Method I:
Method II:
Method III:
Reaction scheme mentioned above will hereafter discussed in more detail.
method I
In method I, perfluorination diiodo-compound and vinylidene fluoride VDF react the α fluoridized with forming section, ω-diiodo-compound.
In one embodiment, perfluorination diiodo-compound is formula ICF
22r
fcF
2the alpha, omega diiodo perfluo-compound of I, wherein R
ffor divalent perfluorinated linking group.The commercially available acquisition of alpha, omega diiodo perfluo-compound or use technology as known in the art obtain.In one embodiment; perfluor disulfonyl base fluorochemical can be reduced, and then with Iod R to form perfluorination diiodo-compound, as such as U. S. application 61/715; disclosed in 413 (being filed in 10-18-2012), this application is incorporated herein by reference.In another embodiment, by making Propylene oxide hexafluoride and Iod R to prepare alpha, omega diiodo perfluo-alkane, disclosed in such as U. S. application 61/715059 (being filed in 10-17-2012), this application is incorporated herein by reference.Alternatively, by comprise prepare alpha, omega diiodo perfluo-alkane currently known methods to prepare alpha, omega diiodo perfluo-alkane, such as TFE telomerization.But telomerization method may be unfavorable for forming the carbon chain lengths of odd number, it can be expectation in some cases.
In one embodiment, perfluorination diiodo-compound comprises heteroatoms in circular part and/or branching and/or chain.Usually, perfluorination linking group (R
f) comprise at least 1,2,3,4,5,7 or even 9 carbon atoms.In one embodiment, perfluorination linking group is straight chain.In another embodiment, and if can to comprise the branched groups with 1 to 5 carbon atom enough large for perfluorination linking group, also cyclic group is comprised.In the embodiment of alternative, perfluorination linking group comprises heteroatoms in chain, such as nitrogen, sulphur or oxygen.
Exemplary perfluorination diiodo-compound comprises formula I (CF
2)
athe alpha, omega diiodo perfluo-alkane of I, wherein a is at least 3 and the integer of at the most 20 (that is, a be 3,4,5,6,7 etc.), such as I (CF
2)
3i, I (CF
2)
4i, I (CF
2)
5i, I (CF
2)
6i, I (CF
2)
7i and I (CF
2)
8i.
In the reaction of method I, vinylidene fluoride (VDF, CF
2=CH
2) be inserted in perfluorination diiodo-compound.In order to realize the insertion of VDF, free radical is used to form compound, light (such as ultraviolet radiation) and/or heating.
Exemplary free radical forms compound and comprises superoxide or azo-compound.Superoxide comprises such as organo-peroxide, such as diacyl peroxide, peroxyester, dialkyl peroxide and hydrogen peroxide.Azo-compound comprises such as, azo isobutyronitrile and azo-2-cyanopentanoic acid.It is electron donor that other free radical forms compound, such as the metal known in document or metal complexes and part.This type of exemplary electronic donor with the interpolation of the perfluorination iodine of unsaturated C-C is Cu, Zn, Mg, Pd (0), Fe, Ni, Pt (P (C
6h
5)
3)
4, Ir (CO) H (P (C
6h
5)
3)
3, Pb (C
2h
3o
2)
4with RhCl (P (C
6h
5)
3)
2.
In one embodiment, reaction can at least 10,25,50,100 or even 125 DEG C; The highest by 140,150,200 or even carry out at the temperature of 220 DEG C.
In one embodiment, carry out with pure substance with the reaction of VDF.In another embodiment, carry out in the presence of the solvent with the reaction of VDF.Typical solvent comprises inert solvent, such as, the solvent fluoridized such as can trade(brand)name " 3M perfluorotributylamine conductance liquid (3M FLUORINERT ELECTRONIC LIQUID) " and " 3M NOVEC Engineered Fluid (3M NOVEC ENGINEERED FLUID) " from 3M company (the 3M Co. of St. Paul, MN, St.Paul, MN) buy those.
In one embodiment, the ratio of perfluorination diiodo-compound and VDF is 1:2.5 to 2.5:1.As shown in the exemplary reaction of method I above, when being inserted in perfluorination diiodo-compound by VDF, 1:1 adducts can be formed (such as, formula I) or 1:2 adducts is (namely, the perfluorination diiodo-compound of 1 equivalent and the VDF of 2 equivalents, such as, formula II).The ratio of adjustable VDF and perfluorination diiodo-compound is to be conducive to specific adducts.Such as, in order to be conducive to forming 1:1 adducts, the ratio of perfluorination diiodo-compound and VDF is 1:0.8 to 1:1.1.In order to be conducive to forming 1:2 adducts, the ratio of perfluorination diiodo-compound and VDF is 1:1.8 to 1:2.5.In addition, can control and optimizing reaction conditions (comprising temperature, reaction times, pressure and/or stirring velocity) to be conducive to specific adducts.
Be separated by known method and the perfluor diiodide (that is, partially fluorinated α, ω-diiodo-compound) of the VDF of purifying gained replacement.
Carbon number in the α that gained is partially fluorinated, ω-diiodo-compound is identical with two carbon that the carbon number existed in perfluorination diiodo-compound raw material adds from VDF.Therefore, method I as disclosed can be used to generate odd number with the partially fluorinated α of even number, ω-both diiodo-compounds, this depends on the carbon length of initial feed.Such as, if alpha, omega diiodo perfluo-alkane comprises three CF
2group, then the partially fluorinated α of gained, ω-diiodo-alkane will have four CF
2group and a CH
2group.Equally, if alpha, omega diiodo perfluo-alkane comprises four CF
2group, then the partially fluorinated α of gained, ω-diiodo-alkane will have five CF
2group and a CH
2group.In addition, if perfluorination diiodo-compound comprises-CF
2cF (CF
3) CF
2-part, the then partially fluorinated α of gained, ω-diiodo-compound also will comprise-CF
2cF (CF
3) CF
2-part adds CH
2cF
2group.
In one embodiment, the partially fluorinated α prepared by the method for method I, ω-diiodo-compound comprises following those: I (CF
2)
xcH
2cF
2i; ICF
2cH
2(CF
2)
xcH
2cF
2i, wherein x be selected from 3,5,7,9 or 1 odd-integral number; And the combination of these formulas.
In one embodiment, the α that the sample portion obtained by method mentioned above is fluoridized, ω-diiodo-compound comprises I (CF
2)
3cH
2cF
2i, I (CF
2)
4cH
2cF
2i, I (CF
2)
5cH
2cF
2i, ICF
2cH
2(CF
2)
3cH
2cF
2i, ICF
2cH
2(CF
2)
4cH
2cF
2i, ICF
2cH
2(CF
2)
5cH
2cF
2i and their combination.
In one embodiment, partially fluorinated α, ω of the present disclosure-diiodo-compound can be used as chain-transfer agent in Macroscopic single crystal, or, as will be described, can be used for generating other fluorinated compound.
In the disclosure, with alkali or class alkali cpd, the perfluorination diiodo-compound that the VDF from method I replaces can be processed further with dehydrofluorination in non-protic organic solvent.
method II
In method II, by partially fluorinated α, the iodine olefin(e) compound (that is, the side of molecule comprises end atomic iodine and comprise the compound of end carbon-to-carbon double bond on the opposite side of molecule) that ω-diiodo-compound dehydroiodination is fluoridized with forming section.This type of partially fluorinated iodine olefin(e) compound can be used as cure site monomer.
In method II, partially fluorinated α, ω-diiodo-compound is the 1:1 adducts from method I, and then its experience dehydroiodination is to remove HI from molecule, thus forms end carbon-to-carbon double bond.
In general, alkalescence or the class basic cpd of at least one molar equivalent should be used to the perfluor diiodide of VDF replacement, to be conducive to the iodine olefin(e) compound that forming section is fluoridized.
Alkalescence and class basic cpd comprise as known in the art those, such as, the dimethyl formamide solution etc. of methylate, KOH, NaOH, alkylamine, LiCl.
In one embodiment, reaction can at least 10,20,23,25,30 or even 35 DEG C; The highest by 70,80,90,100,150,200 or even carry out at the temperature of 220 DEG C.
In one embodiment, reaction is carried out in the presence of the solvent.Typical solvent comprises such as aprotic organic solvent such as butyronitrile and dimethyl formamide.
Be separated and the partially fluorinated end iodine olefin(e) compound of purifying gained by known method.
In one embodiment, the partially fluorinated iodine olefin(e) compound obtained by the method for method II comprises those of formula (III): I (CF
2)
acH=CF
2, wherein a be greater than 2 and be not more than 20 integer.In one embodiment, formula III is I (CF
2)
acH=CF
2, wherein a be selected from 3 to 11 odd-integral number (in other words, 3,5,7,9 or 11).
The iodine olefin(e) compound that sample portion is fluoridized comprises: I (CF
2)
ycH=CF
2; Wherein y be greater than 2 and be not more than 20 integer, such as I (CF
2)
3cH=CF
2, I (CF
2)
4cH=CF
2, I (CF
2)
5cH=CF
2, I (CF
2)
6cH=CF
2, and their combination.
In one embodiment, partially fluorinated end iodine olefin(e) compound of the present disclosure can be used as cure site monomer in Macroscopic single crystal.
method III
In method III, partially fluorinated α, the iodine olefin(e) compound that ω-diiodo-compound is fluoridized with forming section by dehydroiodination (namely, the side of molecule comprises end atomic iodine and on the opposite side of molecule, comprises the compound of end carbon-to-carbon double bond), partially fluorinated diolefin compound (that is, the opposite side of molecule comprising the compound of two end carbon-to-carbon double bonds) or their combination.Partially fluorinated iodine olefin(e) compound can be used as cure site monomer, and partially fluorinated diolefin compound can be used as monomer simultaneously.
In method III, partially fluorinated α, ω-diiodo-compound is the 1:2 adducts from method I, and then its experience dehydroiodination is to remove HI from molecule, thus forms end carbon-to-carbon double bond.In method III, this can betide partially fluorinated α, the one or both ends of ω-diiodo-compound.
Dehydroiodination uses the reaction conditions in alkali or class alkali cpd and method II as described above to carry out.
As shown in the exemplary reaction in method III above, when carrying out dehydroiodination, the one or both ends of partially fluorinated α, ω-diiodo-compound (such as, likes II) can dehydroiodination, thus obtains such as according to the compound of formula IV and V.In addition, the ratio of adjustable alkali and class alkali cpd and the partially fluorinated compound of α, ω-diiodo-is to be conducive to specific product.Such as, in order to be conducive to forming formula IV, the ratio of the equivalent of the compound that α, ω-diiodo-is partially fluorinated and alkali and class alkali cpd is 1:0.8 to 1:1.1.In order to be conducive to forming formula V, the ratio of the equivalent of the compound that α, ω-diiodo-is partially fluorinated and alkali and class alkali cpd is 1:1.8 to 1:2.5.
Be separated and the partially fluorinated compound of purifying gained by known method.
In one embodiment, the partially fluorinated iodine olefin(e) compound obtained by the method for method III comprises those of formula (IV): CF
2=CH (CF
2)
acH
2cF
2i, wherein a be greater than 2 and be no more than 20 integer (such as, 3,4,6,8, etc.).In one embodiment, formula IV is ICF
2cH
2(CF
2)
acH=CF
2, wherein a be selected from 3 to 11 odd-integral number (in other words, 3,5,7,9 or 11).
The iodine olefin(e) compound that sample portion is fluoridized comprises: CF
2=CH (CF
2)
xcH
2cF
2i, wherein x be selected from 3 to 11 odd-integral number (in other words, 3,5,7,9 or 11).The iodine olefin(e) compound that sample portion is fluoridized comprises: ICF
2cH
2(CF
2)
3cH=CF
2, ICF
2cH
2(CF
2)
4cH=CF
2, ICF
2cH
2(CF
2)
5cH=CF
2, ICF
2cH
2(CF
2)
6cH=CF
2, and their combination.
In another embodiment, partially fluorinated diolefin compound is obtained by the method for method III, all those such as formula (V): CF
2=CH (CF
2)
acH=CF
2, wherein a be greater than 2 and be not more than 20 integer.In one embodiment, formula V is CF
2=CH (CF
2)
acH=CF
2, wherein a be selected from 3 to 11 odd-integral number (in other words, 3,5,7,9 or 11).
The diolefin compound that sample portion is fluoridized comprises: CF
2=CH (CF
2)
ycH=CF
2, wherein y be greater than 2 and be not more than 20 integer.The diolefin compound that sample portion is fluoridized comprises: CF
2=CH (CF
2)
3cH=CF
2, CF
2=CH (CF
2)
4cH=CF
2, CF
2=CH (CF
2)
5cH=CF
2, CF
2=CH (CF
2)
6cH=CF
2, and their combination.
In one embodiment, partially fluorinated end iodine olefin(e) compound of the present disclosure can be used as cure site monomer in Macroscopic single crystal, and partially fluorinated diolefin compound of the present disclosure can be used as monomer in Macroscopic single crystal.
macroscopic single crystal
In one embodiment, compound as disclosed herein (such as, formula I, II, III, IV and V those) can be used alone in fluoropolymer polymerization or use together with the additional alkene fluoridized.
In fluoropolymer preparation, the compound of formula I, II, III, IV and/or formula V can be polymerized to form fluoropolymer (in other words, comprising the polymkeric substance of fluorine atom along main polymer chain) with one or more fluorinated olefinic monomer.
Fluorinated olefinic monomer is the monomer having carbon-to-carbon double bond and comprise at least one fluorine atom, and is those monomers except those the partially fluorinated compounds synthesized herein.In other words, they are and those different monomers belonging to formula III, IV and V disclosed herein.Fluorinated olefinic monomer can be perfluorination (or complete fluoridized) or partially fluorinated (comprising at least one hydrogen atom and a fluorine atom).
Exemplary perfluorination olefinic type monomers comprises: R 1216 (HFP), tetrafluoroethylene (TFE), trifluorochloroethylene (CTFE), perfluor (alkyl vinyl ether), trifluorochloroethylene, perfluor (methylvinylether) (PMVE), perfluor (propyl vinyl ether) (PPVE), perfluor (methoxypropyl vinyl ether), perfluor (ethoxyl methyl vinyl ether), CF
2=CFOCF
2cF
2cF
2oCF
3, CF
2=CFOCF
2oCF
2cF
2cF
3, CF
2=CFOCF
2oCF
2cF
3, CF
2=CFOCF
2oCF
3, and their combination.
The olefinic type monomers that sample portion is fluoridized comprises: vinyl fluoride (VF), vinylidene fluoride (VDF), five fluorine propylene (such as, 2-hydrogen five fluorine propylene), trifluoro-ethylene and their combination.
Outside fluorinated olefinic type monomers, also can add nonfluorinated olefinic type monomers.Exemplary non-fluorinated olefinic type monomers comprises: propylene, ethene, iso-butylene and their combination.In general, these monomers added are by with the fluoropolymer being less than 25 % by mole, be preferably less than 10 % by mole and be even less than 3 % by mole to use.
Fluoropolymer as herein described obtains by making partially fluorinated compound polymerization of the present disclosure under the existence of fluorinated olefinic monomer and optional additional monomer.Known polymerization technique can be used, comprise aqueous emulsion polymerization.
Reaction vessel for aqueous emulsion polymerization technique normally can bear the pressure vessel of internal pressure during polyreaction.Usually, described reaction vessel will comprise mechanical stirrer, and it can make reactor content fully mix and produce heat exchange system.The fluorochemical monomer of any amount can be loaded in reaction vessel.Monomer can be added in batches or in continuous or semi-continuous mode.The independent speed that each monomer is added in still will depend on specific monomer wear rate in time.Preferably, to add speed identical with monomer consumption speed (namely monomer changes the speed of polymkeric substance into) for monomer.
In one embodiment, can use fluorinated surfactant, it corresponds to following general formula:
Y-R
f-Z-M
Wherein Y represents hydrogen, chlorine or fluorine; R
frepresent straight chain or the branching perfluoroalkylene groups with 4 to 10 carbon atoms; Z represents COO
–or SO
3 –, and M represents alkalimetal ion or ammonium ion.This type of fluorinated surfactant comprises fluorinated alkanoic acids and fluorinated alkane sulfonic acid and their salt, the ammonium salt of such as Perfluorocaprylic Acid and Perfluorooctane sulfonates.Also imagining for the preparation of polymkeric substance as herein described is the fluorinated surfactant of following general formula:
[R
f-O-L-COO
-]
iX
i +
Wherein L represents partially fluorinated or complete fluoridized alkylidene group or the aliphatic hydrocarbon group of straight chain, R
frepresent the partially fluorinated or complete fluoridized aliphatic group of straight chain or the partially fluorinated or complete fluoridized group being inserted with one or more Sauerstoffatom of straight chain, X
i +representative has the positively charged ion of valency i, and i is 1,2 and 3.Object lesson is described in the U.S. 2007/0015937, and it is incorporated herein by reference.
Also imagining is fluorinated polyether tensio-active agent for the preparation of polymkeric substance described herein, such as United States Patent (USP) 6,429, and described in 258.
In one embodiment, polyreaction is substantially free of emulsifying agent.This type of emulsifying agent can comprise the paraffinic acid and salt thereof that the emulsifying agent fluoridized such as fluoridizes; The alkansulfonic acid fluoridized and salt thereof; Fluorine oxyethyl chain alkanoic acid and salt thereof; And their combination.As used herein, be substantially free of the emulsifying agent that emulsifying agent means to be less than relative to the gross weight of the dispersion existed 0.05%, 0.01% or even 0.001 % by weight, or even in the dispersion of gained, emulsifying agent do not detected.
Also chain-transfer agent can be loaded in reaction vessel.In general, chain-transfer agent is added polyreaction to control the molecular weight of the polymer chain grown.Available chain-transfer agent comprises C
2-C
6hydrocarbon (such as ethane), alcohol, ether, comprise the ester of alphatic carboxylic acid ester and malonic ester, ketone and halohydrocarbon.Useful especially chain-transfer agent is the dialkyl ether of such as dme and methyl tertiary butyl ether and so on.During polyreaction can also continuously or semi continuous mode carry out adding of chain-transfer agent.Exemplary chain-transfer agent comprises: (i) C1-C10 alpha, omega diiodo perfluo-alkane; (ii) I (CF
2)
zcH
2cH
2i, wherein z is the even-integral number of 2 to 10; (iii) CH
2i
2; (iv) I (CF
2)
zcH
2i, wherein z is the even-integral number of 2 to 10; And (v) their combination.Exemplary chain-transfer agent comprises 1,3-diiodo perfluo propane, Isosorbide-5-Nitrae-diiodo perfluo butane, 1,6-diiodo perfluo hexane and 1,8-diiodo perfluo octane.
Also cure site monomer can be added reactor, described cure site monomer is impregnated in polymkeric substance during polyreaction, and is then used as site and is cross-linked subsequently to make polymer chain.This type of cure site monomer can comprise nitrile group-containing group, bromine and/or iodine.This type of cure site monomer is well known in the art, and can comprise such as bromine difluoroethylene, bromotrifluoethylene, iodine trifluoro-ethylene, bromo-2, the 2-difluoroethylenes of 1-and bromo-3,3,4, the 4-tetrafluoro butylene of 4-, CF
2=CFO (CF
2)
5cN, CF
2=CFOCF
2cF (CF
3) OCF
2cF
2cN, CF
2=CFOCF
2cF (CF
3) OCF
2cF (CF
3) CN, CF
2=CFOCF
2cF
2cF
2oCF (CF
3) CN, CF
2=CFOCF
2cF (CF
3) OCF
2cF
2cN; And their combination.
When using the cure site monomer of formula III and/or IV during polyreaction, the chain-transfer agent of formula I and/or II may be used, and/or chain-transfer agent is selected from (i) C1-C10 alpha, omega diiodo perfluo-alkane; (ii) I (CF
2)
zcH
2cH
2i, wherein z is the even-integral number of 2 to 10; (iii) CH
2i
2; (iv) I (CF
2)
zcH
2i, wherein z is the even-integral number of 2 to 10; And (v) their combination.
Usually, after initially adding monomer, initiated polymerization is carried out by initiator or initiator system being joined in aqueous phase.Such as, superoxide can be used as radical initiator.The specific examples of peroxide initiator comprises: hydrogen peroxide, diacyl peroxide (as diacetyl peroxide, two propiony peroxide, dibutyryl superoxide, dibenzoyl peroxide, benzoyl acetyl peroxide, diamyl acid peroxide, dilauryl peroxide) and other water soluble per-acids and their water-soluble salt are as ammonium salt, sodium salt or sylvite.The example of peracid comprises peracetic acid.Also can use the ester of peracid, its example comprises tert-butyl peroxy acetate and t-butylperoxy pivarate.Available another kind of initiator is water miscible azo-compound.The redox system being suitable as initiator comprises the combination of (such as) peroxydisulfate and sulphite or bisul-phite, peroxydisulfate and the combination of peroxydisulfate or the combination of peroxydisulfate and hydrazine.Other available initiator is the ammonium salt of persulfuric acid, permanganic acid or mangaic acid, an alkali metal salt or alkaline earth salt, or mangaic acid.Based on the gross weight of polymerization reaction mixture, the consumption of initiator usually between 0.03 % by weight and 2 % by weight, preferably between 0.05 % by weight and 1 % by weight.The initiator of full dose can be added when being polymerized and starting, or in a continuous manner initiator can be added between polymerization period in polyreaction until reach 70% to 80% transformation efficiency.Also can add part initiator when reacting and starting, then during polyreaction, remainder is disposable or merotomize and add.Also accelerator can be added, such as the water-soluble salt of iron, copper and silver.
At polyreaction initiating stage, usually the reactor of sealing and content thereof are preheated to temperature of reaction.Polymerization temperature can from 20 DEG C, from 30 DEG C or even from 40 DEG C, and paramount 100 DEG C, paramount 110 DEG C or even paramount 150 DEG C can be reached further.The scope of polymerization pressure such as can be 4 to 30 bar, especially 8 to 20 bar.Described aqueous emulsion polymerization system also can comprise auxiliary agent, such as buffer reagent and complex-forming agents.
The amount of polymer solids that can obtain at the end of polymerization be generally at least 10 % by weight, or even at least 20 % by weight, and at the most 40 % by weight, and even at the most 45 % by weight; And the mean particle size of gained fluoropolymer is usually between 50nm and 500nm.
After polymerization, polymeric dispersions can condense and be washed, and forms polymer latex just as is known in the art such.
In one embodiment, relative to the gross weight of polymer latex, polymkeric substance of the present disclosure comprises the iodine of at least 0.05,0.1,0.2 or even 0.4 % by weight.In one embodiment, relative to the gross weight of polymer latex, polymer latex of the present disclosure comprises the iodine of at the most 0.5,0.75,1 or even 1.5 % by weight.
Polymer latex of the present disclosure is partially fluorinated polymkeric substance.As disclosed herein, partially fluorinated polymkeric substance comprises at least one hydrogen atom and at least one fluorine atom on the main chain of polymkeric substance.
Exemplary fluoropolymer comprises: TFE/ propylene copolymer, TFE/ propylene/VDF multipolymer, VDF/HFP multipolymer, TFE/VDF/HFP multipolymer, TFE/PMVE multipolymer, TFE/CF
2=CFOC
3f
7multipolymer, TFE/CF
2=CFOCF
3/ CF
2=CFOC
3f
7multipolymer, TFE/CF
2=C (OC
2f
5)
2multipolymer, TFE/ ethyl vinyl ether (EVE) multipolymer, TFE/ butyl vinyl ether (BVE) multipolymer, TFE/EVE/BVE multipolymer, VDF/CF
2=CFOC
3f
7multipolymer, ethene/HFP multipolymer, TFE/HFP multipolymer, CTFE/VDF multipolymer, TFE/VDF multipolymer, TFE/VDF/PMVE/ ethylene copolymer and TFE/VDF/CF
2=CFO (CF
2)
3oCF
3multipolymer.
solidification
In an embodiment of the present disclosure, fluoropolymer of the present disclosure can solidify with peroxide firming agent (comprising organo-peroxide).In many cases, the tert-butyl peroxide with the tertiary carbon atom being attached to peroxy oxygen is preferably used.
Exemplary superoxide comprises: 2,5-dimethyl-2,5-bis-(tert-butyl peroxy base) hexane; Dicumyl peroxide: two (2-tert-butylperoxyiso-propyl) benzene; Dialkyl peroxide; Two (dialkyl peroxide); 2,5-dimethyl-2,5-bis-(t-butyl peroxy) 3-hexin; Benzoyl peroxide; Peroxidation 2,4 dichloro benzene formyl; T-butylperoxyl benzoate; α, α '-bis-(t-butyl peroxy-diisopropyl benzene); Tert-butylperoxyiso-propyl carbonate, t-butyl peroxy 2-ethylhexyl carbonate, t-amyl peroxy 2-ethylhexyl carbonate, tertiary hexyl peroxy isopropyl base carbonate, two [1,3-dimethyl-3-(t-butyl peroxy) butyl] carbonate, carbon peroxy acid, O, O'-1,3-glyceryl OO, two (1, the 1-dimethyl ethyl) esters of O ' O'-and their combination.
The amount of the peroxide firming agent of general use will be every 100 parts of fluoropolymers at least 0.1,0.2,0.4,0.6,0.8,1,1.2 or even 1.5; 2,2.25,2.5,2.75,3,3.5,4,4.5,5 or even 5.5 weight parts at the most.
In Peroxide cure systems, usually expect to comprise auxiliary agent.Those skilled in the art can select conventional auxiliary agent based on the physical property expected.Exemplary auxiliary agent comprises: tricarbimide three (methyl) allyl ester (TMAIC), triallyl isocyanurate (TAIC), cyanuric acid three (methyl) allyl ester, poly-triallyl isocyanurate (poly-TAIC), triallyl cyanurate (TAC), xylylene-bis-(diallyl isocyanurate) (XBD), N, N'-meta-phenylene bismaleimide, Phthalic acid, diallyl ester, three (diallyl amine)-s-triazine, triallyl phosphite, 1, 2-polyhutadiene, glycol diacrylate, diethylene glycol diacrylate, and their combination.Another kind of available auxiliary agent is by formula CH
2=CH-R
f1-CH=CH
2represent, wherein R
f1can be the perfluorinated alkylidene of 1 to 8 carbon atom.This analog assistant provides the physical strength of enhancing to the final elastomerics solidified.They are generally with every 100 parts of fluoropolymers at least 0.5,1,1.5,2,2.5,3,4,4.5,5,5.5 or even 6; The amount of maximum 4,4.5,5,5.5,6,7,8,9,10,10.5 or even 11 weight parts uses.
Fluoro-containing copolymer composition also can comprise be generally used for elastic composition preparation in polytype additive (such as pigment, filler (such as carbon black), pore-forming material and as known in the art those).
Metal oxide is traditionally in peroxide cure.Exemplary metal oxide comprises: Ca (OH)
2, CaO, MgO, ZnO and PbO.In one embodiment, curable fluoropolymer substantially go up not containing metal oxide (that is, in every 100 parts of fluoroelastomers, described composition account for be less than 1,0.5,0.25,0.1 or even less than 0.05 part).In one embodiment, curable fluoropolymer comprises metal oxide.Such as, every 100 parts of fluoropolymers at least 1.5,2,4,5 or even 6 parts of metal oxides.
In solidification process of the present invention, by conventional equipment (such as two roller mill) at high temperature compounding fluoropolymer glue together with the superoxide of aequum, auxiliary agent and other component.Then fluoropolymer glue processed and shaping (such as, with the shape of flexible pipe or flexible pipe liner) or molded (such as, with the form of O shape ring).Then can the goods of hot briquetting, to solidify glue composition and to form the elastomeric article of solidification.
The fluoropolymer of solidification especially can be used as being exposed to sealing member, packing ring and the moulded piece in the system (such as automobile, chemical treatment, semi-conductor, aerospace and petroleum industry application etc.) of high temperature and/or caustic material.Because fluoropolymer can be used in sealing applications, so it is well important that polymkeric substance shows under compression.Compression seal is easily compressed based on elasticity physical efficiency and is produced the anti-ability of making a concerted effort pushing away matching surface.Material is passed in time in a variety of environmental conditions and is kept this ability of making a concerted effort to be important for permanent stability.Due to thermal expansion, stress relaxation and thermal ageing, initial sealing force is passed in time and will be failed.By determining the sealing force kept, can assess elastomer material under a set of conditions, such as 200 DEG C, 225 DEG C, 250 DEG C and sealing force even under the hot conditions of 275 DEG C keep particularly.
Exemplary embodiment of the present disclosure comprises:
Embodiment 1: a kind of composition comprising partially fluorinated compound, it is selected from:
(a)I(CF
2)
xCH
2CF
2I;
(b)ICF
2CH
2(CF
2)
xCH
2CF
2I;
(c)I(CF
2)
yCH=CF
2;
(d) CF
2=CH (CF
2)
ycH
2cF
2i; With
(e)CF
2=CH(CF
2)
yCH=CF
2
Wherein x be selected from 3 to 11 odd-integral number, and y be greater than 2 integer.
Embodiment 2: a kind of polymer composition, it comprises the polymeric reaction product of following reactant:
(a) first compound, described first compound is selected from the partially fluorinated compound described in embodiment 1; With
B () second compound, described second compound comprises the olefinic type monomers fluoridized.
Embodiment 3: according to the polymer composition of embodiment 2, wherein the second compound is selected from: R 1216, trifluoro-ethylene, vinyl fluoride, vinylidene fluoride, tetrafluoroethylene, perfluor (methylvinylether), perfluor (propyl vinyl ether), perfluor (methoxypropyl vinyl ether), perfluor (ethoxyl methyl vinyl ether), trifluorochloroethylene and their combination.
Embodiment 4: the polymer composition any one of embodiment 2 or 3, wherein reactant also comprises (c) chain-transfer agent, and its Chain transfer agent is selected from: C1-C10 alpha, omega diiodo perfluo-alkane; I (CF
2)
zcH
2cH
2i, wherein z be greater than 2 integer; CH
2i
2; I (CF
2)
zcH
2cF
2i, wherein z be greater than 2 integer; And their combination.
Embodiment 5: according to the polymer composition of embodiment 4, its Chain transfer agent is 1,3-diiodo perfluo propane or Isosorbide-5-Nitrae-diiodo perfluo butane.
Embodiment 6: the polymer composition any one of embodiment 2 to 5, at least one wherein in x or y is 3.
Embodiment 7: the polymer composition any one of embodiment 2 to 6, wherein reactant also comprises (d) nonfluorinated olefinic type monomers.
Embodiment 8: the polymer composition any one of embodiment 2 to 7, wherein polymer composition comprises the iodine of 0.05 to 1 % by weight.
Embodiment 9: a kind of goods, it comprises the cured polymer compositions according to any one of embodiment 2 to 8.
Embodiment 10: a kind of method preparing polymkeric substance, it comprises:
C () provides the first fluorinated olefinic monomer, described first fluorinated olefinic monomer comprises partially fluorinated Compound I (CF
2)
ycH=CF
2, wherein y for described in embodiment 1 be greater than 2 integer; Second fluorinated olefinic monomer; And initiator; And
D () makes the first fluorinated olefinic monomer and the polymerization of the second fluorinated olefinic monomer to form polymkeric substance under the existence of initiator.
Embodiment 11: a kind of method preparing polymkeric substance, it comprises:
A () provides the first fluorinated olefinic monomer, described first fluorinated olefinic monomer comprises partially fluorinated Compound C F
2=CH (CF
2)
ycH=CF
2, wherein y be embodiment 1 be greater than 2 integer; Second fluorinated olefinic monomer; And initiator; And
B () makes the first fluorinated olefinic monomer and the polymerization of the second fluorinated olefinic monomer to form polymkeric substance under the existence of initiator.
Embodiment 12: the method any one of embodiment 10-11, it is polymerized under being also included in the existence of chain-transfer agent.
Embodiment 13: according to the method for embodiment 12, its Chain transfer agent is 1,3-diiodo perfluo propane or Isosorbide-5-Nitrae-diiodo perfluo butane.
Embodiment 14: the method any one of embodiment 10-13, wherein the second fluorinated olefinic monomer is selected from: R 1216, trifluoro-ethylene, vinyl fluoride, vinylidene fluoride, tetrafluoroethylene, perfluor (methylvinylether), perfluor (propyl vinyl ether), perfluor (methoxypropyl vinyl ether), perfluor (ethoxyl methyl vinyl ether), trifluorochloroethylene and their combination.
Embodiment 15: the method any one of embodiment 10-14, wherein the first fluorinated olefinic monomer and the second fluorinated olefinic monomer are polymerized in emulsion polymerization.
Embodiment 16: the method any one of embodiment 10-15, wherein polymerization procedure is substantially free of emulsifying agent, and wherein emulsifying agent is selected from the paraffinic acid and salt thereof fluoridized; The alkansulfonic acid fluoridized and salt thereof; Fluorine oxyethyl chain alkanoic acid and salt thereof; And their combination.
Embodiment 17: a kind of method preparing partially fluorinated compound, it comprises makes formula I (CF
2)
xthe molecule of I and vinylidene fluoride react to form I (CF
2)
xcH
2cF
2i, wherein x be selected from 3 to 11 odd-integral number.
Embodiment 18: according to the method for embodiment 17, it also comprises makes I (CF
2)
xcH
2cF
2i dehydrogenation iodate is to form formula I (CF
2)
xcH=CF
2partially fluorinated iodine olefin(e) compound, wherein x be selected from 3 to 11 odd-integral number.
Embodiment 19: a kind of method preparing partially fluorinated compound, it comprises makes formula I (CF
2)
xthe molecule of I and vinylidene fluoride react to form ICF
2-CH
2(CF
2)
ycH
2cF
2i, wherein y be greater than 2 integer.
Embodiment 20: according to the method for embodiment 19, it also comprises makes ICF
2-CH
2(CF
2)
ycH
2cF
2i dehydrogenation iodate is to form (i) formula CF
2=CH (CF
2)
ycH
2cF
2the partially fluorinated diolefin of I; (ii) formula CF
2=CH (CF
2)
ycH=CF
2partially fluorinated diolefin; And (iii) their combination, wherein y be greater than 2 integer.
example
Following examples further illustrate advantage of the present disclosure and embodiment, but the concrete material quoted in these examples and amount thereof and other condition and details should not be interpreted as limiting the present invention undeservedly.Except as otherwise noted, otherwise in these examples, all per-cent, ratio and ratio are all by weight.
Otherwise all material all can from the Sigma-Aldrich chemical company of such as Milwaukee, Wisconsin State (Sigma-Aldrich Chemical Company unless otherwise mentioned or obviously; Milwaukee, WI) commercially available, or be that those skilled in the art are known.
These are used to abridge in following instance: g=gram, min=minute, mol=mole, hr=hour, mL=milliliter; Wt=weight.
material
1
h/
19
f-NMR characterizes
Use Varian VNMRS 400FT-NMR spectrograph (Varian Associates, Inc. (US) 611 Hansen Way, Palo Alto, California 94303, U.S.A. (Varian Inc. of California Paro Otto, Palo Alto, CA)) obtain 1D and 2D FT-NMR spectrum for compositional analysis, described spectrograph at the temperature of about 22-23 DEG C with 5mm oppositely-detect together with gradient probe and run.
solidification rheological
Use uncured compounded samples, according to ASTM D 5289-95, use rheometer (by alpha's technology (Alpha Technology of the Danisco A/S BJ Rep Office in sub-Krona city, Ohio, A Dynisco Company, Akron, OH) Alpha Technology RPA 2000, with mobile mould rheometer (MDR) pattern), without preheating, 177 DEG C, under 12min elapsed time and 0.5 degree of radian, be cured rheological characteristics test.When there is no platform or peak torque (MH), measure the minimal torque (ML) and peak torque that obtain during the time period of specifying.Also measure the time (ts2) that moment of torsion increases by 2 units above ML; Moment of torsion reaches the time (t ' 50) of the value equaling ML+0.5 (MH-ML); The time (t ' 90) of ML+0.9 (MH-ML) is reached with moment of torsion, and the loss tangent (δ) at MH and ML place.Report the test is in table 1.
physical property
According to ASTM D1646-06 type A, at 121 DEG C, use ectotrochanter (ML 1+10) (can Ohioan alpha's technology (the Alpha Technologies of purchased from American by MV 2000 apparatus, Ohio, USA)), mooney viscosity or compound mooney viscosity is measured.Result is reported with mooney unit.
example 1: prepare 1,3-diiodo-HFC-236fa by HFPO
(can from the superpressure portion of New Port scientific & technical corporation of Maryland State Jie Sepu (Superpressure Division of Newport Scientific Inc. by 300mL Hastelloy (Hastelloy) B-2 autoclave, Jessup, MD) commercially available) load 24.5g iodine and 2.5g nickel catalyzator.Autoclave is loaded nitrogen and finds time three times.With dry ice, autoclave is cooled down, and load the HFPO of 58g.Autoclave is placed in vibrator, and in described vibrator, autoclave is heated to 170 DEG C and continues 12h.Before being discharged by the gas of generation, make autoclave be cooled to room temperature, and obtain 36g adopting dark liquid.Pass through
19f and
1h NMR (nucleus magnetic resonance) analyzes crude mixture, obtains following result: I-CF
2-I (0.0036 absolute weight %), I-(CF
2)
2-I (<0.00005%), I-(CF
2)
3-I (92.2%), I-(CF
2)
4-I (0.41%), I-(CF
2)
5-I (5.4%), I-(CF
2)
8-I (0.27%) adds a small amount of other iodine various and diiodo-compound, partially fluorinated compound, sour fluorochemical, carboxylic acid, alkene etc.
example 2: by FSO
2
c
4
f
8
sO
2
f prepares Isosorbide-5-Nitrae-diiodo-Octafluorobutane
By adding 76g (2.0mol) sodium borohydride in the 2-propyl alcohol of 600g, by 186g (0.5mol) perfluorinated butane disulfonyl base fluorochemical FSO in the 3 liter of 3 neck round-bottomed flask being equipped with mechanical stirrer, condenser, feed hopper and thermopair
2c
4f
8sO
2f reduces.Completed in three hours and add speed, temperature of reaction is remained on less than 40 DEG C.After adding, reaction be heated to 75 DEG C and continue one hour.Reaction is cooled to 25 DEG C, and adds 33% sulfuric acid of 298g, carry out afterwards filtering to obtain HOSOC
4f
8sO
2h solution.3 liter of 3 neck round-bottomed flask is loaded 300g (1.19mol) iodine, 282g (1.19mol) Sodium Persulfate, 500g distilled water and 500g through stirring and being heated to the 2-propyl alcohol of 55 DEG C.HOSOC is added in one hour
4f
8sO
2h solution.After adding, reaction be heated to 75 DEG C and keep one hour.By reactor mixture being heated to paramount 108 DEG C, the distillment of product and solvent is collected in receptor.With sodium sulfite treatment product and solvent mixture (10% aqueous solution of 70g) to obtain pale yellow solution.Add additional water to obtain fluorochemicals, to form lower floor's phase, and with 100g distilled water, fluorochemicals product is washed twice.Vacuum distilling obtains 147g (0.33mol) Isosorbide-5-Nitrae-diiodo-Octafluorobutane I-C
4f
8-I, it has the boiling point of 85 DEG C/100 holders for 66% productive rate confirmed by F and HNMR.
example 3:CF
2
=CH-C
3
f
6
the preparation of-I
By the Parr of 600ml
tMreactor is found time and is loaded 250g (0.62mol) 1,3-diiodo-HFC-236fa I-C
3f
6-I (being obtained by example 1) and 12g (0.06mol) tertiary butyl-2-ethyl hexanoate superoxide, and stir.Reactor is heated to 75 DEG C, and under 40psi, in four hours, adds 30g (0.47mol) vinylidene fluoride add and make it react 20h.By reactor cooling to 25 DEG C, and 269g product mixtures is discharged from reactor.Vacuum distilling obtains 126g (0.27mol) ICF
2cH
2c
3f
6i, it seethes with excitement under 125 DEG C/90 holder vacuum.Higher boiling is cut and is mainly comprised 46g (0.09mol) ICF
2cH
2c
3f
6cH
2cF
2i.126g (0.27mol) ICF making the Tributylamine of the amount of 95g (0.51mol) and add in two hours
2cH
2c
3f
6i reacts.Temperature of reaction reaches 45 DEG C, and after being cooled to 25 DEG C, adds the 20%H of 250g
2sO
4.Vacuum distilling under 90 DEG C/90 holder vacuum is distilled water outlet and is comprised the CF of about 91%
2=CH (CF
2)
3i, 4.1% CF
2=CH (CF
2)
3cH=CF
2, 1.0% CF
3cH
2(CF
2)
3i, 1.0% CF
2=CH (CF
2)
3cH
2cF
2i (the CF of H and 0.3%
2)
3the mixture of I.64g (0.19mol) had 1-iodine 1,1,2,2,3,3,5, the 5-octafluoro amylene IC of 94 DEG C of boiling points
3f
6cH=CF
2based on vinylidene fluoride with 40% productive rate be separated.Inner CFCl
319FNMR chemical shift (-) ppm High-Field, ICF2 (a) CF2 (b) CF2 (c) CH=CF2 (d, e), a:-58.1, t/t; B:-115.5, m; C:-106.9, m; D:-71.2, d/t; E:-72.7, d/t; The low field of 1HNMR (+) ppm of inner TMS ,-CH (f)=CF2, f:4.67, d/t.
example 4:CF
2
=CH-C
4
f
8
the preparation of-I
By the Parr of 600ml
tMreactor is found time and is loaded 398g (0.88mol) Isosorbide-5-Nitrae-diiodo-Octafluorobutane I-C
4f
8-I (being obtained by example 2) and 38g (0.18mol) tertiary butyl-2-ethyl hexanoate superoxide, and stir.Reactor is heated to 72 DEG C, and under 40psi, in six hours, adds 30g (0.47mol) vinylidene fluoride and make it react 20h.By reactor cooling to 25 DEG C, and 439g product mixtures is discharged from reactor.Vacuum distilling obtains 159g (0.31mol) ICF
2cH
2c
4f
8i, it seethes with excitement under 105 DEG C/17 holder vacuum.Additional vacuum distilling obtains 87g (0.16mol) ICF
2cH
2c
4f
8cH
2cF
2i, it seethes with excitement under 150 DEG C/1 holder vacuum.117g (0.23mol) ICF making the Tributylamine of the amount of 83g (0.44mol) and added in two hours
2cH
2c
4f
8i reacts.Temperature of reaction reaches 38 DEG C, and after being cooled to 25 DEG C, adds the 20%H of 250g
2sO
4.Vacuum distilling under 90 DEG C/90 holder vacuum is distilled water outlet and is comprised the CF of about 94.1%
2=CH (CF
2)
4i, 1.7% CF
2=CH (CF
2)
4cH=CF
2, 0.8% CF
3cH
2(CF
2)
4i, 0.6% CF
3cH=(CF
2)
3i (the CF of I and 0.4%
2)
4the mixture of I.By iodo-1,1,2,2,3,3,4,4,6, the 6-ten fluorine hexene IC of 56g (0.14mol) 1-with 126 DEG C of boiling points
4f
8cH=CF
2based on vinylidene fluoride with 30% productive rate be separated.Inner CFCl
319FNMR chemical shift (-) ppm High-Field, ICF2 (a) CF2 (b) CF2 (c) CF2 (d) CH=CF2 (e, f), a:-58.8, t/t; B:-113.0, m; C:-123.3; D:-108.6; E:-71.0, d/m; F:-72.2, d/m; The low field of 1HNMR (+) ppm of inner TMS ,-CH (g)=CF2, g:5.85, d/q.
example 5:CF
2
=CH-C
4
f
8
the preparation of-I
By the Parr of 600ml
tMreactor is found time and is loaded 375g (0.83mol) Isosorbide-5-Nitrae-diiodo-Octafluorobutane I-C
4f
8-I (being obtained by example 2), and stir.Reactor is heated to 206 DEG C, and under 98psi, in 11 hours, adds 52g (0.81mol) vinylidene fluoride and make it react one hour.By reactor cooling to 25 DEG C, and 410g product mixtures is discharged from reactor.Vacuum distilling obtains 152g (0.29mol) ICF
2cH
2c
4f
8i, it seethes with excitement under the vacuum of 105 DEG C/17 holders.145g (0.28mol) ICF making the Tributylamine of the amount of 98g (0.52mol) and add in one hour
2cH
2c
4f
8i reacts.Temperature of reaction reaches 53 DEG C, and after being cooled to 25 DEG C, adds the 33%H of 150g
2sO
4.Stir the mixture and be separated.To bottoms mutually in add 100g distilled water.Vacuum distilling distillation water outlet under 90 DEG C/90 holder vacuum and based on vinylidene fluoride yield be 24% iodo-1,1,2,2,3,3,4,4,6, the 6-ten fluorine hexene IC of 76g (0.19mol) 1-
4f
8cH=CF
2.
example 6:CF
2
=CH-C
4
f
8
-CH=CF
2
preparation
87g (0.16mol) CF making the Tributylamine of the amount of 83g (0.44mol) and add in one hour
2cH
2c
4f
8cH
2cF
2i (being obtained by example 4) reacts.Temperature of reaction reaches 48 DEG C, and after being cooled to 25 DEG C, adds the 20%H of 250g
2sO
4.Vacuum distilling under 90 DEG C/90 holder vacuum is distilled water outlet and is comprised the CF of about 60.9%
2=CH (CF
2)
4cH=CF
2, 20.2%ofCF
2=CH (CF
2)
4i, 8.2%CF
3cF
2(CF
2)
4i (the CF of I and 0.05%
2)
4the mixture of I.25g (0.08mol) 1,1,3,3,4,4,5,5,6,6,8, the 8-ten difluoro octadiene CF of 92 DEG C of boiling points will be had
2=CH-C
4f
8cH=CF
2be separated.19FNMR chemical shift (-) the ppm High-Field of inner CFCl3, CF2 (a, b)=CHCF2 (c) CF2 (d) CF2 (d) CF2 (c) CH=CF2 (a, b), a:-71.4, d/m; B:-72.6, d/m; C:-108.6, m; D:-124.0, m; The low field of 1HNMR (+) ppm of inner TMS ,-CH (g)=CF2, g:4.64, d/t.
example 7: the preparation of fluoroelastomer
4 liters of reactors are loaded 2,250 grams of water, 2 grams of ammonium persulphate (APS, (NH4) 2S2O8) and 8 grams of dipotassium hydrogen phosphate (K2HPO4) 50% aqueous solution, 3.5 grams HFE-7500 and 3.5 gram obtained in example 3 above separated product, described separated product comprises the CF containing about 91%
2=CH (CF
2)
3i, 4.1% CF
2=CH (CF
2)
3cH=CF
2, 1.0% CF
3cH
2(CF
2)
3i, 1.0% CF
2=CH (CF
2)
3cH
2cF
2i (the CF of H and 0.3%
2)
3the mixture of I.Found time by reactor, the destroyed and reactor nitrogen pressurization of described vacuum is to 25psi (0.17MPa).By this vacuum and pressure process in triplicate.After removing oxygen, reactor be heated to 80 DEG C and destroy vacuum, then using R 1216 (HFP) to be forced into 40psi (0.28MPa).Then reactor is loaded tetrafluoroethylene (TFE), vinylidene fluoride (VDF) and R 1216 mentioned above (HFP), thus make reactor pressure reach 200psi (1.38MPa).Total the preloading of TFE, VDF and HFP is respectively 25.8 grams, 78.9 grams and 243.6 grams.Stirred reactor under 650rpm.Because the monomer consumption in polyreaction makes reactor pressure reduce, therefore need TFE, VDF and HFP to send into reactor continuously, under remaining on 200psi (1.38MPa) to make pressure.The ratio of HFP/VDF and TFE/VDF is respectively 0.61 and 0.23 by weight.After 4.5 hours, stop sending into monomer, and by reactor cooling.The dispersion of gained has the solids content of 31.2 % by weight and the pH of 3.3.Dispersion particle size is 240nm, and the total amount of dispersion is 3,873 grams.
For coagulum, the dispersion obtained according to the method described above by 942g adds the MgCl of 1.25 % by weight of 2,320mL
2in the aqueous solution.By by coagulum, by cheese cloth, also extruding to remove unnecessary water gently reclaims micelle.Send micelle back to coagulation vessel, and amount to flushing 3 times with deionized water.Final rinse and filter after, by micelle in 130 DEG C of baking ovens dry 16 hours.Gained fluoroelastomer rubber has the mooney viscosity of 53 at 121 DEG C.There is provided FT-IR to analyze, this fluoroelastomer contain the TFE copolymerization units of 16.0 % by weight, the VDF copolymerization units of 48.9 % by weight and 33.2 % by weight HFP copolymerization units.Oil repellent is 67.8 % by weight.
Use 6 " two roller mills, by by from part fluoroelastomer rubber of 100 above and 30 parts of N990 carbon blacks, 2 part of 2,5-dimethyl-2,5-bis-(t-butyl peroxy)-hexane and 3 parts of TAIC mixtures, prepare fluoroelastomer compound.
By using Alpha Technology RPA 2000 with the uncured compounding mixture of the program test described in MDR (mobile disc type rheometer) pattern and ASTM D 5289-95, carry out the solidification rheological of study sample.Fluoroelastomer compounds exhibit goes out good curing characteristics, and 90% set time, (t ' 90) were 0.1.6 minute, and δ moment of torsion (MH-ML) is 8.1lb-in (9.2dNm).Test result is summarized in table 1.
table 1
Example 7 | |
Solidification rheological characteristics (MDR) 12min@177 DEG C | |
ML(in-lb) | 0.8 |
MH(in-lb) | 8.9 |
Δ moment of torsion (in-lb) | 8.1 |
ts2(min) | 0.6 |
t'50(min) | 0.8 |
t'90(min) | 1.6 |
tanδML | 1.4 |
tanδMH | 0.259 |
When not departing from the scope and spirit of the present invention, will be apparent for a person skilled in the art about foreseeable amendment of the present invention and change.In order to exemplary purpose, the present invention should not be limited to this embodiment shown in application.If have conflict or contradiction between the disclosure in this specification sheets and any file of being incorporated herein by reference, be then as the criterion with this specification sheets.
Claims (10)
1. a composition, it comprises partially fluorinated compound, and described partially fluorinated compound is selected from:
(f)I(CF
2)
xCH
2CF
2I;
(g)ICF
2CH
2(CF
2)
xCH
2CF
2I;
(h)I(CF
2)
yCH=CF
2;
(i) CF
2=CH (CF
2)
ycH
2cF
2i; With
(j)CF
2=CH(CF
2)
yCH=CF
2
Wherein x be selected from 3 to 11 odd-integral number, and y be greater than 2 integer.
2. a polymer composition, it comprises the polymeric reaction product of following reactant:
(a) first compound, described first compound is selected from partially fluorinated compound according to claim 1; With
B () second compound, described second compound comprises the olefinic type monomers fluoridized.
3. polymer composition according to claim 2, wherein said second compound is selected from: R 1216, trifluoro-ethylene, vinyl fluoride, vinylidene fluoride, tetrafluoroethylene, perfluor (methylvinylether), perfluor (propyl vinyl ether), perfluor (methoxypropyl vinyl ether), perfluor (ethoxyl methyl vinyl ether), trifluorochloroethylene and their combination.
4. the polymer composition according to any one of Claims 2 or 3, wherein said reactant also comprises (c) chain-transfer agent, and wherein said chain-transfer agent is selected from: C1-C10 alpha, omega diiodo perfluo-alkane; I (CF
2)
zcH
2cH
2i, wherein z be greater than 2 integer; CH
2i
2; I (CF
2)
zcH
2cF
2i, wherein z be greater than 2 integer; And their combination.
5. the polymer composition according to any one of claim 2 to 4, at least one wherein in x or y is 3.
6. goods, it comprises the cured polymer compositions according to any one of claim 2 to 5.
7. prepare a method for polymkeric substance, it comprises:
A () provides the first fluorinated olefinic monomer, described first fluorinated olefinic monomer comprises partially fluorinated Compound I (CF
2)
ycH=CF
2, wherein y is the integer being greater than 2 according to claim 1; Second fluorinated olefinic monomer; And initiator; And
B () makes described first fluorinated olefinic monomer and the polymerization of the second fluorinated olefinic monomer to form polymkeric substance under the existence of described initiator.
8. prepare a method for polymkeric substance, it comprises:
A () provides the first fluorinated olefinic monomer, described first fluorinated olefinic monomer comprises partially fluorinated Compound C F
2=CH (CF
2)
ycH=CF
2, wherein y is the integer being greater than 2 according to claim 1; Second fluorinated olefinic monomer; And initiator; And
B () makes described first fluorinated olefinic monomer and the polymerization of the second fluorinated olefinic monomer to form polymkeric substance under the existence of described initiator.
9. prepare a method for partially fluorinated compound, it comprises makes formula I (CF
2)
xthe molecule of I and vinylidene fluoride react to form I (CF
2)
xcH
2cF
2i, wherein x be selected from 3 to 11 odd-integral number.
10. prepare a method for partially fluorinated compound, it comprises makes formula I (CF
2)
xthe molecule of I and vinylidene fluoride react to form ICF
2-CH
2(CF
2)
ycH
2cF
2i, wherein y be greater than 2 integer.
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CN116171287A (en) * | 2020-09-09 | 2023-05-26 | Agc株式会社 | Method for producing iodine-containing compound, and iodine-containing compound |
CN116171287B (en) * | 2020-09-09 | 2024-04-02 | Agc株式会社 | Method for producing iodine-containing compound, and iodine-containing compound |
Also Published As
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WO2014093024A1 (en) | 2014-06-19 |
EP2931693A1 (en) | 2015-10-21 |
EP2931693B1 (en) | 2020-03-18 |
EP2931693A4 (en) | 2016-05-11 |
US9452960B2 (en) | 2016-09-27 |
US20160185693A1 (en) | 2016-06-30 |
JP2016504446A (en) | 2016-02-12 |
JP6223464B2 (en) | 2017-11-01 |
CN104918906B (en) | 2018-07-13 |
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